Fungicidal preparations containing benzimidazole compounds

ABSTRACT

The invention relates to fungicidal benzimidazolyle derivatives of the general formula   D R A W I N G These new compounds are very effective as ingredients in biocidal preparations for plant-protection and combating insects, acarides, nematodes.   WHEREIN R1, R2 and R3 may be identical or different and each represents hydrogen, halogen, alkyl, alkoxy, alkylthio, alkylSO-, alkylSO2-, -NO2, -CN, CF3, CHO, COOR&#39;&#39;,

United States Patent [191 Janiak et al.

[ FUNGICIDAL PREPARATIONS CONTAINING BENZIMIDAZOLE COMPOUNDS [75] Inventors: Stefan Janiak, Basel; Otto Rohr,

Therwil, both of Switzerland [73] Assignee: Ciba-Geigy AG, Basie, Switzerland [22] Filed: Jan. 10, 1972 [21] Appl. No.: 216,783

Related US. Application Data [62] Division of Ser. No. 769,699, Oct. 22, 1968, Pat. No.

[30] Foreign Application Priority Data UNITED STATES PATENTS 3,65 2,5 80

Primary Examiner-Albert T. Meyers Assistant Examiner-D. W. Robinson Attorney, Agent, or Firm-Harry Falber; Frederick H. Rabin 5 7 ABSTRACT The invention relates to fungicidal benzimidazolyle derivatives of the general formula 3/1972 Janiak etal ..260/309.2

7 [4 June 28, 1974- wherein R R and R may be identical or different and each represents hydrogen, halogen, alkyl, alkoxy, alkylthio, alkylSO-, alkylSO N0 -CN, CF CHO, COOR',

SO:N

wherein R and R" each represents hydrogen or lower alkyl and R represents hydrogen or'an aliphatic or cycloaliphatic residue, X= O, S, -Nl-lor N-alkyl and R represents an aliphatic, araliphatic or aromatic residue.

These new compounds are very effective as ingredients in biocidal preparations for plant-protection and combating insects, acarides, nematodes.

6 Claims, N0 Drawings FUNGICIDAL PREPARATIONS CONTAINING BENZIMIDAZOLE COMPOUNDS This is a division of application Ser. No. 769,699, filed on Oct. 22, 1968, now US. Pat. No. 3,652,580.

The present invention provides compounds of the general formula CHO, COOR',

-CON I represents an aliphatic, araliphatic or aromatic residue.

The present invention also provides a pesticidal preparation which comprises, as active ingredient, at least one compound of the general formula I given above, together with a suitable carrier.

The preparation may contain one or more of the following additives: a solvent, a diluent, an emulsifier, a dispersing agent, a thickener, an adhesive as well as other known pesticides.

The active substances defined by formula I possess various interesting biocidalproperties. They not only act as herbicides and defoliants, but at lower concentrations, at which no phytotoxic side effects arise, they show a strong lethal action on various representatives of the order acarina (ticks, spider mites and the like), insects and soil insects, their eggs and larvae, storage pests, for example cockroaches, snails and their eggs, nematodes, plant-pathogenic fungi, bacteria and viruses.

The symbol R in the general formula of this invention is defined as hydrogen or an aliphatic or cycloaliphatic residue. The aliphatic residue may be saturated or unsaturated and preferably represents a lower alkyl residue; it may furthermore be interrupted by 0, S, S0, S0, and the like, and may optionally also contain cyano, carboxamido or carbalkoxy groups. Perhalogenated aliphatic residues are excluded by this definition. Possible cycloaliphatic residues are, above all, cycloalkyl residues for example, the cyclopropyhcyclobutyl, cyclopentyl or cyclohexyl residue.

R, in the general formula in this: invention is defined as an aliphatic, araliphatic or aromatic residue; the aromatic residue, preferably phenyl, may be substituted in i the most diverse manner, for example, by halogen atoms, or alkyl, alkoxy or alkylthio residues, or by the groups -NO,, -CN, CF, and the like. If R, is an aliphatic residue, it may be interrupted by O or S, and preferably represents lower alkyl residues.

Examples of compounds in accordance with the ini vention, are compounds of formula:

t which have anespecially good herbicidal action. In this formula R,, R, and R have the significance mentioned 1 .above, with R, and R, preferably representing hydrogen, lower alkyl, halogen alkyl or NO, and R, representing hydrogen, lower alkyl or cycloalkyl; R,l represents hydrogen or lower alkyl and R, represents i lower alkyl, phenyl, alkylphenyl or halogenalkylphenyl.

H H H CH, CH, H H CH, t CH, CH, H H Cyclopropyl H CH, H H Cyclopropyl CH, CH, H H H CH, H H C,H, CH, CH, H H C,H H CH, H H C,H, CH, CH, Cl H H CH, CH, Cl H CH, H CH, Cl H CH, CH, CH, Cl H Cyclopropyl H CH, Cl H Cyclopropyl CH, CH, Cl H C,H, H CH, Cl H C,H, CH, CH, Cl H C,H, H CH, Cl H C,H, CH, CH, Cl H CH, H C,H, Cl CI CH, H CH, Cl Cl CH, CH, CH, NO, H H CH, CH, NO, H CH, CH, CH, NO, H Cyclopropyl ,H CH, NO, H Cyclopropyl CH, CH, NO, H H CH, NO, H H, CH, CH, NO, H C,H H CH, NO, H C,H CH, CH, N0, H CH, H CH, CF, H H CH, CH, CF, H CH, H CH, CF, H CH, CH, CH, CF, H C,H, H CH, CF, H C,H, CH, CH, CF, H C,H, H CH, CF, H C,H, CH, CH, CF, H CH, H C,H, CH, H H CH, CH, CH, H CH, H CH, CH, H CH, CH, CH, CH, H Cyclopropyl H CH, CH, H Cyclopropyl CH, CH, CH, H C,H, H CH, CH, H C,H, CH, CH, CH, H C,H, H CH, CH C,H, Cllli, CH,

The compounds, for exampleof formula III H H H n s H H H C,,H,Cl,(3.4) H H H C,H,C H,( m) H H H C a H H H C,H H H H C;,H, H H CH, CH; H H CH C,H H H CH C H Cl H H C,H,Cl,(3,4) Cl H H C,H,C H,( m) Cl H H C,H,, Cl H H C H, Cl H CH, C,H,Cl,( 3 ,4) Cl H CH, C,H,CH,(m) Cl H CH;, C,H Cl H CH C H, No, H H -c,H,c1, 3,4 N H H C,H,C H,( m) NO, H H C,H, No H H c,H, N0, H CH C H,Cl,( 3 ,4) NO, H CH, C,H,CH,( m) NO, H CH C,H CH, H H c,H,c|, 3,4 CH: H H CsH CH;(m) C H: H H C,H CH H H Y C,H C H;, H CH C,,H ,Cl,( 3 ,4) CH, H CH, C,H,CH,( m) CH, H C H, C H CH H C H, CH1, CF, H H C H,

CF, H H C,H;,Cl,(3,4) CF, H H C.,H,C H,( m) CF; H H CH, CF 3 H H C,H CF, H H C,H, CF H CH, C,H CF, H CH, C,H Cl,(3,4) cF H cH c,H,cH, m) CF, H CH, C,H C F, H CH, C,H, H H Cyclopropyl C,H NO, H Cyclopropyl C l-l CH, H Cyclopropyl C,H, NO, H Cyclopropyl C H, CH H Cyclopropyl CH Cl H Cyclopropyl C H Cl H Cyclopropyl C,H,Cl,( 3 ,4)

Cl H Cyclopropyl C.H,CH,(m) Cl H Cyclopropyl C H, Cl H Cyclopropyl C,H (n) Cl H Cyclopropyl C,H (i Cl H Cyclopropyl C,H,NO,( p) Cl H Cyclopropyl C H,( n) Cl H Cyclopropyl Benzyl Cl Cl Cyclopropyl CH, Cl Cl Cyclopropyl C H Cl Cl Cyclopropyl Benzyl The active substances of formula I represent benzimidazolylurethanes,thiolurethanes and -ureas.

They may be manufactured according to the methods usual for the preparation of this class of substances.

As a rule, the procedure followed is to react a benzimidazolyl derivative of formula R1 N Rag C-R4 with a compound of formula wherein A and B are groups which are able to form the grouping whilst undergoing elimination or condensation.

In general, the procedure followed will be to react, in optional sequence, a reactive derivative of carbonic acid or thiocarbonic acid with an imidazole of formula IV (A H) and an amine of formula V (B NH or NH-alkyl) or an alcohol or phenol of formula V (B OH).

industrially, the procedure followed for the formation of the ureas will be to react an imidazole of formula IV (A H) with an isocyanate or a carbamic acid chloride, whilst in the manufacture of urethanes an imidazole of formula IV is reacted with the desired chlorocarbonate.

The new preparations can be applied in many different forms, for example, in the form of sprays, dusting powders and granules. They can also be worked directly into the soil, optionally together with fertilisers.

Possible materials for the manufacture of directly sprayable solutions of the compounds of general formula l are, for example: mineral oil fractions of high to medium boiling range, for example, Diesel oil or kerosene, coal tar oil and oils of vegetable or animal origin,

as well as hydrocarbons, for example, alkylated naphthalenes, or tetrahydronaphthalene, optionally using xylene mixtures, cyclohexanols, ketones, and furthermore chlorinated hydrocarbons, for example, trichlorethane and tetrachlorethane, trichlorethylene or trichlorobenzenes and tetrachlorobenzenes. It is advantageous to use organic solvents having boiling points above 100 C.

it is especially appropriate to prepare aqueous forms for application from emulsion concentrates, pastes or wettable spraying powders by adding water. Possible emulsifiers or dispersing agents are non-ionic products, for example, condensation products of aliphatic alcohols, amines or carboxylic acids having a long-chain hydrocarbon residue of about to carbon atoms with ethylene oxide, for example, the condensation product of octadecyl alcohol and to mols of ethylene oxideor that of soya fatty acid and 30 mols of ethylene oxide or that of technical oleylamine and i5 mols of ethylene oxide or that of dodecylmercaptan and i2 mols of ethylene oxide. Amongst the anionic emulsifiers which may be employed, there may be mentioned: the sodium salt of dodecyl alcohol sulphuric acid ester, the sodium salt of dodecylbenzenesulphonic acid, the potassium or triethanolamine salt of oleic acid or of ab ietic acid or of mixtures of these acids, or the sodium salt of a petroleum-sulphonic acid. Possible cationic dispersing agents that can be used are quaternary ammonium compounds, for example, cetylpyridinium bromide or dihydroxyethylbenzyldodecylammonium chloride.

In order to manufacture dusting and scattering agents, it is possible to use, as solid carriers: talc, kaolin, bentonite, calcium carbonate, calcium phosphate, also charcoal, cork powder, wood flour and other materials of vegetable origin. It is also advantageous to manufacture the preparations in a granular form. The various forms in which the preparations can be used may, in the usual manner, he provided with additions of substances which improve the distribution, adhesion rain resistance or penetrating power; as such substances fatty acids, resin,,glue, casein or alginates may be mentioned.

The preparations according to the invention may be employed by themselves or together with usual pesticides, especially insecticides, acaricides, nematocides, bactericides or further fungicides and/or herbicides.

The following Examples illustrate the invention:-

EXAMPLE 1 a. Urea type 38.6 g of 2-cyclopropyl-5 (6)-chlor obenzimidazole are dissolved in 210 ml of chloroform in a three-necked flask. After adding 5 g of magnesium oxide and 70 ml of water, 22 g of methyl chloroformate are added drop by drop at l 5 C., while stirring well. When the reaction has subsided, the mixture is stirred for a further hour, after which the organic phase is separated off in a separating funnel, washed with 25 ml of water and dried over sodium sulphate. The solvent is distilled off,

and the residue recrystallised from acetone/water.

Melting point: 57-6l" [compound No. 2].

The following compounds were also manufactured in an analogous manner:

G-Rt R:

N R0 O=-N No. R, R, R, R, [R Melting point "C 3 H H CH, H CH, l64-l67 4 H H CH, H C,H, l24-l26 5 H H CH; H C.H,CF -,(m) l30-l39 6 N0, H H H CH, l43-l45 7 N0, H CH H CH, 2l5-2l7 8 NO, H H H C H l79-l8l 9 CF; H CH H CH; l43-l49 10 CH, CH; H H CH, 144-]46 C-R4 N Q=-" 0B-s No. R, R R Melting point "C ll H CH, C H 103-105 12 H CH, C H;Cl,(3.4) 124-]27 13 H CH, C;H CH;(m) ll5-ll7 l4 H CH5 C I-LNOHP) l53-l57 [5 H C H; Benzyl -8! [6 H CH C H.(n) 3840 I7 Cl H GHg 80-88 l8 Cl H CH -95 l9 Cl CH; C H 30-93 20 Cl CH; CH, 48-55 2| Cl C Hfln) CHQ l00-l0l 22 Cl C H (n) C;H, (i) Oil 23 Cl C;H (n) CH; 80-35 24 NO, H C H -l05 25 --NO, H CH, 1 19-125 26 NO, CH; CJ-l l27-l32 27 NO, CH; CH; [37-142 28 CH, H CHg Oil 29 cu H CH, on 30 CH, CH; C H 90-99 3i CH, CH, CH; Oil 32 CF; CH, CH; 86-90 33 Cl Cyclopropyl CJ-h 87-88 34 H do. CH; 38-40 35 CI do. CH, 57-61 Eek-sea A 20 strength wetting powder is manufactured from compound No. l in the following manner: 20 g of active substance are very finely ground in a pin mill together with 8 g of fine precipitated silicon dioxide (commercially available under the name Zeosil) as well as with 64 g of Bolus alba, 5.6 g of a condensation product of 1 mol of p-tert. octylphenol with about 8 mols of ethylene oxide and 2.4 g of sodium 2- heptadecyll -benzylimidazole-di-sulphonate. The powder thus obtained can be worked up with water in any desired amount, to give stable dispersions.

EXAMPLE 3 Compound No.

an amount of 2 kg of active substance/ha. The application took place 12 days after sowing the test plants, when these had developed 1 to 2 genuine leaves. I

10 was applied in the postemergence process to the test plants listed-below using Digitaria Beta Chrysanthemum Linum Brassica Stellaria Amaranthus Soya Cotton l plant undamaged plant no longer viable 9 plant killed.

EXAMPLE 4 The urethanes listed in Example 1 showed a good action against weeds in the pre-emergence and in the postemergence process.

The following results were achieved for compounds Nos. 33 and 35:

Pre-emergence Post-emergence No. 35 No. 33 No; 35 No. 33 Plant kg 5kg 10kg 5kg 5kg 2kg 5kg 2kg Avena 9 6 7 5 5 4 5 2 Setaria 9 6 9 7 5 3 8 4 Sinapis 9 9 9 9 9 9 9 9 Lepidium 9 9 9 8 9 9 9 9 l no damage 5 plant no longer viable 9 plant completely dead.

EXAMPLE 5 Compound No. 23 was tested for its action against powdery mildew fungi. Courgette plants (Cucurbita Pepo L.) were grown in a green house and sprayed once prophylactically with an aqueous broth of the compound containing increasing quantities of active substance. Two days after the treatment, the plants were infected with spores of Eryiphe cichoracearum DC, and after 12-14 days the plants were rated as regards 5 fungal attack.

Hereupom a lower inhibitory concentration of PR"! q asi yss lzstanssW I PPS We'claim:

1. A fungicidal composition comprising (1) a fungii9 effective q r lsie awrevnqefrhs smile wherein R represents lower alkyl, phenyl, halogenophenyl, nitrophenyl, lower alkylphenyl or benzyl, and (2) a'suitable fungicidal carrier.

2. A fungicidal composition comprising (1) a fungicidally effective amount of a compound offormula N mg \H I wherein R represents lower alkyl or cycloalkyl having from 3 to 6 ring carbon atoms and R represents lower alkyl, phenyl, halogenophenol, nitrophenyl, lower alkylphenyl or benzyl, and (2) a suitable fungicidal car- 'rier.

3. A fungicidal composition comprising (1) a fungicidally effective amount of the compound of the forand (2) a suitable fungicidal carrier.

4. A method for combatting phytopathogenic fungi which comprises applying thereto a fungicidally effeclive am imt fa m qunq silks .tqrmyla,

3,821,393 r r. 9 10 wherein R represents lower alkyl, phenylj elliyl, phenyl, heloge noph eniil, niirophen yl, lower elhalogenophenyl, nitrophenyl, lower alkylphenyl or lgylphenyl or benzyl. h

benzyl.

A method for combatting phytopathogenic fungi 6. A method for combatting phytopathogenic fungi which comprises applying thereto a fungicidally effec-- 5 which comprises applying thereto a fungicidally effecv m of a m u of the formula i i?KFFQ'JELPEEP?29 3199994 fihsiarmflw.

N N n c1 7 C-R4 c- 0Hmcm n N O=$OR8 0=( -0CH3 M l5 W wherein R represents lower alkyl or cycloalkyl having qm t fir n se h q m1??? arrr P evle i938?" 

2. A fungicidal composition comprising (1) a fungicidally effective amount of a compound of the formula
 3. A fungicidal composition comprising (1) a fungicidally effective amount of the compound of the formula
 4. A method for combatting phytopathogenic fungi which comprises applying thereto a fungicidally effective amount of a compound of the formula
 5. A method for combatting phytopathogenic fungi which comprises applying thereto a fungicidally effective amount of a compound of the formula
 6. A method for combatting phytopathogenic fungi which comprises applying thereto a fungicidally effective amount of the compound of the formula 